Synthetic resin



40 s Th Patented June as, 1932 UNITED STATESPATENT OFFICE ALPEONB 0. OI MOUNT LEBANON, PENNSYLVANIA, ASBIGNDB 1'0 .T EE BELIDIN COMPANY, 01 PITTSBURGH, PENNSYLVANIA,

A CORPORATION O! DELAWARE BYNTKEIIC RESIN e This invention relates to s nthetic resins and more particularly alcohol organicacid type.

In the past many esters of polyhydric alcohols and organic acids and particularlyglycerin and (P01 carb lic acid, such as hthalic anh ri e, ha gbeen prepared and ave acquire a great importance in the resin industry; The simpler ester resins of this y an ydride can be transformed into infusible and insoluble products on heating but tend to be brittle and in many cases show a poor compatibility with nitrocellulose and other cellu ose esters. It has been proposed in the past to modify these particularly monobasic acids, acids and rosin, have achieved great success in commerce, articularly in compositions containing nitrocellulose where their high compatibility'and resins with simple acids, such as fatty desirable roperties have distinguished them-- selves. ere has, however, been some difficulty in the past in obtaining resins of the polyhydric alcohol or nic acid type which are at the same time 0 great strength, satisfactory hardness and light color and which are also ntly, elastic and compatible with nitrocellulose to housed in the coating indust to p we polyhydric alcohol organic acid resins which are hardand can be renderedim I fusible by heating and it is also easy to produce soft resins of thistype compatible with nitrocellulose, but hitherto it has been diflicult to .t e polyhydric such as those of glycerin and phthalic and such modified ester resins -It' is a relatively. simple matter or impossible "to produce compositions in which both desirable. properties are displayedyand in a single eresinthis has been practically unknown. y

' e present-invention covers a new type of polyhydric alcohol organic acid resins many of which can be rendered infusible and have and strength but which 7 show a satisfactory compatibility with nitrocellulose without the use or in some cases withsatisfactory hardness also are elastic and of excessive amounts,

out the use of any, of the ordinary plasticizers.

These resins are prepared by reacting a polyhydric alcohol such as glycerinwith an organic acid, for example, phthalic anhy Application am July 1a, 1081. Serial as. 551,788.

dride, and phthalide or substituted phthalides. 'l he invention includes not only resins containing only single acids, for example a single dicarboxylic acid in addition to the jphthalide, but also includes resins in which other acids are presentsuch as, for example, monocarboxylic acids. The fact that phthalide may be used to replace part of the acids in golyh dric alcohol organic acid resins with esira le improvements in the ph sical and chemical characteristics of the pr ucts opens up a wide field of utility, particularly in combination with cellulose esters. In general the phthalide modified resins are soluble in solvents which will disselve the unmodified resins but owing to the fact that phthalide, which is the lactone of the oxymethyl benzoic acid, contains an aliphatic alcoholic hydroxyl the solubility'of the'products in any solvents is generall unmodifie resins and in some cases hthalide modified resins arev soluble in so vents in which the unmodified resins'do not dissolve at all. This adds a greater flexibility to the use of the resins of the present invention, ar: ticularl in coatingcompositions, as it wi' ens the choice of solvents which can be used.

I While, as 'hasbeen some cases plasticizers may in many phthalides, esters of vketo aromatic acids such as benzoyl and naphthoyl benzoic'acids, etc. V j Among the polyhydrlc alcohols which may be used, glycerinandglycolare'of the greathydric alcohols may be used, singly or in a mixture, with glycerin orglycol, or both. Examples .of such polyhydric alcohols are greater than in the case of the [butylene oxide, chlorhydrines, ethylene oxpointed out'above, in I be eliminatedv from compositions containing phthalide modified resins, it should be understood that cases it is desirable to add plasticiz-. ers, alt ough freqlu'ently the quantity added 'may f-be-considera ly reduced. Any bf the est commercial importance but other polgide, glycerin ethers, polyglycerols, amylene glycol, butylene-i glycol, diethylene glycol,

glycol methyl ether, glycol propyl ether,

polyglycols, propylene glyc 'triethylene 1 pyroracemic, se

- the like may be employed.

glycol, 1- rop lene Flycol, 1-3 propylene glycol, 2-3 uty ene g yfiol, manmtol, man-- nitol ethers, pentaeryt 1te, pentaerythrite ethers. 7 H

Phthalic anhydride is the most common dicarboxylic acid and because of its low price and excellent-characteristics in resins containing it, it is of prime commerclal importance. However, the invention is m no sense limited-to the use of phthalic anhydride as the acid in the resins and on the contrary other acids, both polycarbo lic and monocarboxylic, ture, to replace part or all of the phthalic anh dride.

xamples of the p'olycarboxylic acids which may be used are substituted-phthahc anhydride such as halogen, nitro, or amino;

and adipic, azeolaic, boric, camphoric, citric,

cylic, stearic, dihydroxystearic, stearolic,

toluic, tung oil, rich hydrogenated fatty acids, fat acids of castor oil, fatty acids of hydrogenated castor oil; fat acids of cocoanut oil, corn oil, cottonseed oil, drying oils, nondrying oils, fish oil, linseed oil, mahaden oil, perilla oil. rape-seed oil, soya-bean oil, sunflower seed 0i whale oil; glycerides of oils and fats; mixed fat acids of cocoabutter, castor oil, Japan wax; and heat distilled acids from castor oil, corn oil, cottonseed oil, fish oil, lard, linseed oil, peanut oil, rapeseed oil,

soya-bean oil, tung Oll. V

In addition to unsubstituted phthalide, substituted phthalide such asmono or dialkyl or aryl phthalides, alkylidene phthalides and Similarly, reduction products of phthalide such as hexahydrophthalide are likewise included.

The invention will be illustrated in the following specific examples which give typical embodiments of the invention, it being understood that it is in no way limited to the specific details therein set forth.

Emample'l 1 mol of glycerin is heated at 180 C. with 1 mol of phthalic anhydride until evolution may be used, sing y or in adm1x-- of gas ceases, and 1 mol of phthslide is added and heating continued at 210 C. until a test portion withdrawn on a glass rod solidi- A fies toa hard rpduct which is notsticky.

The resin w n cold is of light color or'substantially colorless, very elastic and is not sticky. It can be drawn and bent without breaking and when heated for several hours at 260 is transformed into an insoluble,

infusible resin which shows excellent toughness, bein far less brittle than a resin prepared un er the same conditionsfrom 1 mol of glycerin and 1 mols of phthalic anhydri e.

The resin in its fusible stage is soluble in solvents for glycerin phthalic resins and can be blended with nitrocellulose with which it shows good compatibility. An impregnat ing varnish is obtained which leaves a film of excellent quality even without the addition of a plasticizer but where maximum flexibility is desired an amount of dibutyl phthalate or ethyl benzoylbenzoate equal to about 53-10% of the resin may be added.

Example 2 A resin is prepared with 10% of phthslide instead of 50% of phthalide, calculated in term of mols. It is less elastic than the resin prepared according to Example 1 but shows a far less brittleness than an unmodified glycerine phthalate resin produced under the same conditions.

Example 3 A resin is prepared according to Example 1 with 1 mol of glycerin, 1 mol phthalic anhydride, ,mol phthalide and mol benzoic acid. A very tough, light-colored resin is obtained which shows a remarkable increase in toughness over a corresponding resin in which all of the phthalide is substituted by benzoic acid.

I Example 4 A resin is prepared with 1 mol of glycerin,

0.75 mol phthalic anhydride, 1 mol phthalide, and 0.5 mol fatty acid of cocoanut oil. The resulting resin is soft, very flexible and of light color. It shows high compatibility with nitrocellulose and can be used without any plasticizer to form satisfactory films when dissolved in a suitable solvent.

Example 5 A. resin is prepared with 1 mol of glycerin or polyglycerols and .75 mol of maleic acid, I mol of phthalide and .5 mol benzoylbenzoic acid. A light-colored, hard, elastic resin is obtained.

Example 6 A resin is prepared and 1 mol of ethylene glycol, 1 mol of phthalic' anhydride and 1 mol of phthalide or hexahydrophthalide. .A soft, balsam-like resin is obtained which is an exmeant.

What is claimed as new is: 1. A synthetic resin of the pplyhydric alcohol organic acid t pe' in whic a portion of the acid is replaced y a hthalide substance.

2. A synthetic resin 0 the polyhydric alcohol organic acid 1: ps in which a portion of the acid 1s replaced y phthalide.

8. A nthetic resin, being the condensation pr uct of at least one polyh dric alcohol, at least one polybasic acid, an at least one phthalide substance.

4. A nthetic resin, being the condensa tion pro not of at least one polyhydric alcohol, at least one'polybasic acid and phthalide.

5. A (synthetic resin-which is the condensation pr not of at least one polyhydric alcohol, at leastone polycarboxylic acid, at least one monocarboxylic acid and a phthalide su ance. r

6. A nthetic resin which is the condensation. pr uct of at least'one olyhydric alcohol, at least one polycarboxy ic acid at least one monocarboxylic acid and phthalide.

7. A synthetic resin, being the condensation product of at least one polyh dric alcm hol, phthalic anhydride and a pht alide substance. I

8. A synthetic resin, beingthe condensation product of at least one polyhydric alco-' hol, phthalic anhydride and phthalide.

9. A synthetic resin, being the condensation product of g1 cerin, phthalic anhydride, and a phtha i e substance.

10. A synthetic resin, bein the condensat on product of glycerin, pht ialic anhydride and phthalide.

11. A the glycerin, phthalic anhydride and phthal- 1de substance are present in approximately equlmolecularproportions.

12. A resinaccording to claim 10, in which the'glycerm, phthalic anhydride and phthalcondense with an amount of .dride insufiicient to react with all of the h .d"tol'9' h'h' resm accor mg 6 am w m thus obtained at about 210 C. a

resin, which com rises bringin about condensation of a o yhydric alcoho with an organic carboxy 0 acid capable of formin a.

'. 15. Amethod'ofpreparingasyntheticresin,

which comprises causing lglycerin to condense with an amount of ht a ic anhydride insuflicient to react wit all of the hydroxyls of the lycerin, adding a phthalide substance at 1.0 suficient to react with the unreacted hydroxyls of the glycerin, and bringing about condensation between thelycerin condensation product and t e phtha ide substance. Y

,16. A method of preparing a synthetic resin, which comprises causing g1 cerin to p t a ic anhydroxyls of the glycerin, adding phthali e at least sufiicient to react with the unreacted hydroxyls of the glycerin, and bringin about condensation between the lycerin p thalic condensation product and p thalide. .17. A method of preparmg a synthetic resin which comprises causing one mol of glycerin to condense with one mol of hthalic anhydride, adding a mol of phtha ids and continuing the condensation.

18. A method according to claim 17, in

which the condensation of the phthalide with the lycerin phthalic anhydride condensation pro uct'takes place at a temperature h her han that employed in condensing the ph alic anhydride with the g1 cerin.

19. A method accordm to 018.1111 17, m which the g1 cerin and p thahc anh dr de are condensed at about 180 C. and ph ahde is condensed with the condensation product Signed at Pittsburgh, Pennsylvania, this 17th dayof Jul 1981- PHONS O. JAEGER.

' lde are present in approximately eqmm'olecular proportions. I

18. A method of preparing, a synthetic bringing about condensation of a polyhydric alcohol with an organic carboxylic acid capable of forming a resin therewith the amount less than suflicient to react with all of the hydroxyls of the polyhydric alcohol, adding an amount of a phthallde substance .at least 3 i? 1 h, i h i .1 h 1 as o e y no co 0 an ing a ut the 152m between the min tion product and the phthalide substance.

14. A method of preparinga the unreacted hy-- cient to hthalic III of the acid being 

